EP0088552A1 - Encapsulation par enrobage par des polyhydroxyborates polymères - Google Patents

Encapsulation par enrobage par des polyhydroxyborates polymères Download PDF

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Publication number
EP0088552A1
EP0088552A1 EP83300912A EP83300912A EP0088552A1 EP 0088552 A1 EP0088552 A1 EP 0088552A1 EP 83300912 A EP83300912 A EP 83300912A EP 83300912 A EP83300912 A EP 83300912A EP 0088552 A1 EP0088552 A1 EP 0088552A1
Authority
EP
European Patent Office
Prior art keywords
gel
php
starch
particles
paste
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP83300912A
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German (de)
English (en)
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EP0088552B1 (fr
Inventor
Donald Trimnell
Baruch Saleh Shasha
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
US Department of Agriculture USDA
United States Department of Commerce
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US Department of Agriculture USDA
United States Department of Commerce
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Publication of EP0088552A1 publication Critical patent/EP0088552A1/fr
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/20—Pills, tablets, discs, rods
    • A61K9/28—Dragees; Coated pills or tablets, e.g. with film or compression coating
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2984—Microcapsule with fluid core [includes liposome]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2984—Microcapsule with fluid core [includes liposome]
    • Y10T428/2985—Solid-walled microcapsule from synthetic polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2984—Microcapsule with fluid core [includes liposome]
    • Y10T428/2985—Solid-walled microcapsule from synthetic polymer
    • Y10T428/2987—Addition polymer from unsaturated monomers only
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2989—Microcapsule with solid core [includes liposome]

Definitions

  • This invention relates to a novel method of encapsulating pesticides and other chemical biological agents for controlling their release and to the compositions prepared thereby.
  • Shasha et al. discloses methods of encapsulation whereby a polyhydroxy polymer xanthate and a coupling agent are reacted from a single phase to form an insolubilized xanthide matrix, thereby entrapping the active agent.
  • the Shasha et al. system has the advantage . of operating in both aqueous and nonaqueous two-phase systems, as well as in single-phase systems in which the matrix-forming materials and the core.material are soluble in the same solvent.
  • Another advantage is that the entire reaction mixture is converted into a solidified mass which is readily dried and ground into a usable product after pressing out excess water. This obviates the recovery from a liquid - medium as necessitated by most coacervation and interfacial polymerization methods.
  • widespread commercial acceptance of the Shasha et al. methods has been hindered by the reluctance of the industry to handle carbon disulfide which is both flammable and toxic.
  • Shasha discloses a system for encapsulating certain types of pesticidal agents by the rapid insolubilization of a starch-containing material alkoxide with a bivalent cation selected from the group of calcium, barium, and strontium. While this system is applicable to water-insoluble agents, it is not particularly suitable for those which are water-soluble, nor for substances susceptible to alkali degradation.
  • the agents are dissolved or dispersed in an aqueous polyhydroxy polymer (PHP) paste, which is reacted at an alkaline pH with boric acid or a boric acid derivative to form a continuous insolubilized matrix gel entrapping discontinuous domains of the agent.
  • PHP polyhydroxy polymer
  • This sytem not only avoids the use of xanthates, but also is operative under mildly alkaline pH's thereby permitting encapsulation of acid-sensitive and most alkali-sensitive chemicals.
  • solids contents far in excess of those permissible with the bivalent cation adduct system of Shasha, supra, dehydration of the final product is facilitated.
  • the primary matrix-forming material be derived from either natural or renewable resources or from inexpensive synthetic sources.
  • Another object of the invention is to provide a product in which the encapsulated substance is sufficiently protected to be safe for handling, controllably released to the environment, and resistant to losses by volatilization, leaching, wind transport, and sunlight decomposition.
  • the polyhydroxy polymers (PHP), suitable as matrix-forming materials in accordance with the invention, include any such polymers which are capable of forming a gel: Included are the natural starches such as cereal and potato starch, and flours containing the same, as well as derivatized and modified starches as known in the art. These starches may be in their original granular form or else they may be partially or completely pregelatinized.
  • Illustrative of other gellable PHP are carboxymethylcellulose (CMC), dextran, xylan, and polyvinyl alcohol.
  • the PHP are prepared for the encapsulation reaction by conversion into an aqueous paste. Pasting of pregelantinized starch is of course readily accomplished by stirring the material into water.
  • the other PHP's are pasted either by heating a dispersion thereof in water or by conversion to an alkoxide with an alkali metal hydroxide.
  • Sodium and potassium hydroxides are the most suitable reagents for alkoxida- tion and will react with PHP's in aqueous suspension at ambient temperature.
  • the ratio of alkali metal:repeating polymer unit employed for this step should be in the range of 1:4 to 1:1, and preferably between 1:3 and 1:2. Levels of alkali greater than 1:1 cause unnecessary occlusion of borate salt in the final product.
  • the PHP in paste form is considered to be in the aqueous phase which will constitute the continuous phase of the encapsulation system.
  • the concentration of the PHP in the aqueous suspension prior to pasting should be maintained within the range of about 10-40% solids, and preferably between about 25 and 35% solids. At the higher concentrations, recovery of the final product is facilitated as described in further detail below.
  • the core material to be encapsulated is mixed with the PHP either prior to or subsequent to pasting by any conventional means of obtaining a relatively uniform distribution. At the higher PHP solids concentrations, incorporation prior to pasting is preferable.
  • the domains of agent which constitute the discontinuous phase of the dispersion should be sufficiently small so as to render the dispersion stable until the paste is insolubilized. It would be within the skill of a person in the art to determine the maximum level at which a particular agent can be effectively loaded into the system. For nearly complete encapsulation, the ratio of agent:PHP on a dry weight basis will typically be in the range of 1:10 to 2:3, though with some agents it may be as high as 1:1.
  • core materials For purposes of performance, effective amounts of core materials depend entirely on the type and characteristics of the core material, on matrix thickness, and on the intended utility of the product.
  • atvolatile liquid to be completely withheld from the environment would be incorporated at a lower level than one to be used as a slow-release pesticide.
  • an effective amount of a suitable biological agent is defined herein as that amount of core material which will achieve the desired result (e.g., attract, repel, or kill pests, release a detectable aroma or flavor, or enhance the growth of plants) when the encapsulated composition containing the effective amount of the agent is placed in the proper environment.
  • Chemical biological agents which are suitable for use herein may be any organic or inorganic solids capable of being finely divided or any liquid, provided that the agent does not interfere with the encapsulating process, and does not react with or dissolve the encapsulating matrix.
  • Particularly envisioned are chemicals and chemical formulations which meet the above criteria and which are classified as a known herbicide, insecticide, fungicide, nematocide, bactericide, rodenticide, molluscicide, acaricide, larvacide, fumigant, animal repellant, insect repellant, plant growth regulator, fertilizer, pheromone, sex lure, flavor composition, or odor composition.
  • herbicides include S-ethyl dipropylcarbamothioate, S-propyl dipropylcarbamothioate, S-propyl butylethylcarbamothioate, S-ethyl cyclohexyl- ethylcarbamothioate, S-ethyl bis(2-methylpropyl)-carbamothioate, S-ethyl hexahydro-l-H-azepine-l-carbo- thioate, S-(2,3,3-trichloro-2-propenyl)-bis(l-methylethyl)carbamothioate, 2,6-dinitro-N,N-dipropyl-4-(trifluoromethyl) benzenamine, N-butyl-N-ethyl-2,6-dinitro-4-(trifluoromethyl) benzenamine, N-(cyclo- .propylmethyl
  • Exemplary fungicides include 3a,4,7,7a-tretra- hydro-2-[(trichloromethyl)thio]-1-H-isoindole-1,3(2H)-dione, 3a,4,7,7a-tetrahydro-2-[(1,1,2,2-tetrachloroethyl)thiol-1-H-isoindole-1,3(2H)-dione, 2,4,5,6-tetra- chloro-l,3-benzenedicarbonitrile, and sodium methyldithiocarbamate.
  • Exemplary insecticides include N-[[(4-chlorophenyl)amino]carbonyl]-2,6-difluorobenzamide, 1,1'-(2,2,2-trichloroethylidene) bis(4-chlorobenzene), 2,2-dimethyl-l,3-benzodioxol-4-yl methylcarbamate, O,O-diethyl O-6-methyl-2-(1-methylethyl)-4-pyrimidinyl phosphorothioate, and O-ethyl-S-phenyl ethylphosphono- dithioate.
  • 1,2-dibromo-3-chloropropane is illustrative of a suitable nematocide.
  • Other compositions suitable as core materials for use in accordance with the invention such as organic and inorganic fertilizers, adjuvants, and the like, will be known to those skilled in the art. Core materials dissolved, emulsified, or otherwise dispersed in solvents or carriers, as well as compatible combinations of the above types of compositions are also easily encapsulated by the instant method.
  • the PHP paste to gel it must be at an alkaline pH, which for purposes of the invention is defined as being greater than about 7.5. If the material were pasted by treatment with a strong hydroxide as previously discussed, the pH will typically be on the order of about 9-11, depending upon the PHP and the biological agent. If, on the other hand, the pasting were effected by heating, the pH can be adjusted by addition of alkali. For agents sensitive-to strongly alkaline conditions, it is recommended that the pH be adjusted to within the range of about 7.5 to 8.5 by means of ammonium hydroxide. Alkali-sensitive agents are also advantageously protected by deferring the adjustment until just prior to or simultaneously with the gelling reaction.
  • the paste is gelled in the presence of the biological agent by the addition of a gelling agent selected from the group of boric acid and boric acid derivatives.
  • a gelling agent selected from the group of boric acid and boric acid derivatives.
  • Boric acid is usually preferred where it is desirable to partially or completely neutralize the paste, particularly if it is strongly basic.
  • suitable derivatives include any of the borates such as sodium metaborate, sodium tetraborate (borax), and annonium pentaborate.
  • the gelling agent may either be predissolved in an aqueous medium or else added as a finely pulverized powder having a particle size of less than about 60 mesh. Its level should be selected to cause sufficient gelation without excessive salt occlusion.
  • the molar ratio of gelling agent:hydroxide will range between 1:5 and 5:1, and preferably between 1:2 and 2:1. It is preferred to rapidly mix the gelling agent with the paste in order to effect an essentially instantaneous reaction.
  • the agent Upon entering into solution the agent reacts with the PHP from a single phase.
  • the temperature is not particularly critical, with gelling readily occurring at ambient conditions. The result is substantially homogeneous rubbery mass analogous to the precursiva dispersion in which, now, discontinuous domains of active ingredient are uniformly dispersed throughout a continuous, insolubilized matrix gel.
  • the recovery procedure is aimed at converting the rubbery mass to discrete, free-flowing, nonagglomerating particles.
  • the matrix gel is admixed with a powdery coating material in a coating:PHP ratio in the range of about 1:10 to about 1:1 on a dry weight basis.
  • a powdery coating material in a coating:PHP ratio in the range of about 1:10 to about 1:1 on a dry weight basis.
  • the level of coating material together with the type and extent of shearing will determine the ultimate particle size.
  • a preferred coating material is ungelatinized pearl corn starch, though other powdery materials such as flours, silicas, clays, and the like as known in the art can advantageously be used.
  • the gel may be broken into small particles and then dehydrated by suspension in an excess of alcohol. Water diffuses from the matrix into the alcohol, with minimal loss of active ingredient. While both methods yield nonagglomerating particles which can be readily sieved and air dried, the coating method is preferred for maximizing the retention of volatile agents. It is believed that the coating material seals the open pores near the particle surface, and that as a rule, there is a direct relationship between the level of addition and the percent volatiles retained. It can be appreciated by the skilled artisan that by proper selection of materials and proportions within the scope of the invention as described above, nearly quantative encapsulation of chemical biological agents is attainable, and the release characteristics of the products can be tailored to exacting specifications.
  • Example 1 was repeated except that 6 g. instead of 18 g. of pearl corn starch was used to coat the product prior to drying.
  • the yield after drying overnight was 78.0 g. with 72% of the particles in the 10-35 mesh range.
  • the product contained 1.35% N, corresponding to 18.2% active ingredient and 84% recovery.
  • a series of compounds was encapsulated by the following general procedure: 45 g. of ungelatinized pearl corn starch was slurried with 70 ml. of water and enough chemical biological agent to give 10 g. of active ingredient. The slurry was pasted with 50 ml. of aqueous NaOH (3.3 g. of NaOH) and then converted to a rubbery gel by blending with 5 g. of boric acid. The gel was mixed with 6 g. of additional pearl corn starch to give particles passing 8 mesh. Table I, below, lists compounds encapsulated and percent recovery of the active ingredient used for the encapsulation.
  • Example 34 was repeated except that 11.4 g. of sodium metaborate was used instead of sodium tetraborate. Yield after drying overnight was 78.0 g. with 83% of the particles in the 10-35 mesh range. The product contained 0.78% N, corresponding to 10.5% active ingredient and 90% recovery. ,
  • pregelatinized corn flour was mixed with 100 ml. of water containing 4 ml. of ammonium hydroxide solution (29% ammonia) until a thick paste formed.
  • Twenty grams of "Eradicane 6.7E” was blended into the paste followed by 30 g. of additional pregelatinized corn flour and then 2 g. of boric acid.
  • a rubbery gel formed which was mixed with two 10-g. portions of pregelatinized corn flour.
  • the yield after drying overnight was 86.3 g. with 78% of the particles in the 12-35 mesh range.
  • the product contained 2.63% S, corresponding to 15.6% active ingredient and 80% recovery.
  • a water suspension of the product (5 g./40 ml.) showed pH 8.2.
  • starch xanthate was prepared by mixing 45 g. of pearl corn starch with 250 ml. of water, gelatinizing the mixture with a solution of 5 g. of sodium hydroxide in 75 ml. of water, mixing the resulting paste with 5 ml. of carbon disulfide and allowed the paste to remain 1 hour at room temperature. Twenty grams of "Sutan Plus 6.7E” was dispersed using a "Waring" blender. A solution of 6.25 g. of concentrated sulfuric acid and 6.25 g. of 30% hydrogen peroxide in 100 ml. of ice water was added to form starch xanthide and coagulate the dispersion. The product was dewatered using a Buchner funnel, pulverized to pass 10 mesh, and air dried overnight.
  • alkali starch w prepared by gelatinizing a mixture of 45 g. of pearl corn starch in 250 ml. of water with a solution of 5 g. of sodium hydroxide in 75 ml. of water. Twenty grams of "Sutan Plus 6.7E" was dispersed into the paste using a "Waring" blender. A solution of 10 g. of calcium chloride in 20 ml. of water was added and mixed until coagulation took place. The resultant mass was dewatered by filtration, pulverized to pass 10 mesh, and air dried overnight.
  • the loss of safener to the extent observed for the procedure of Example 19 may be due to its polymerization during processing, while the additional losses in the xanthide and calcium adduct procedures most likely occurred during filtration.

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Zoology (AREA)
  • Medicinal Chemistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Toxicology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Dispersion Chemistry (AREA)
  • Environmental Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Agronomy & Crop Science (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Epidemiology (AREA)
  • Animal Behavior & Ethology (AREA)
  • Public Health (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Medicinal Preparation (AREA)
  • Manufacturing Of Micro-Capsules (AREA)
  • Colloid Chemistry (AREA)
EP83300912A 1982-02-26 1983-02-22 Encapsulation par enrobage par des polyhydroxyborates polymères Expired EP0088552B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US06/352,662 US4439488A (en) 1982-02-26 1982-02-26 Encapsulation by entrapment within polyhydroxy polymer borates
US352662 1982-02-26

Publications (2)

Publication Number Publication Date
EP0088552A1 true EP0088552A1 (fr) 1983-09-14
EP0088552B1 EP0088552B1 (fr) 1986-11-12

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EP83300912A Expired EP0088552B1 (fr) 1982-02-26 1983-02-22 Encapsulation par enrobage par des polyhydroxyborates polymères

Country Status (26)

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US (1) US4439488A (fr)
EP (1) EP0088552B1 (fr)
JP (1) JPS59500263A (fr)
KR (1) KR880002503B1 (fr)
AU (1) AU564907B2 (fr)
BG (1) BG43351A3 (fr)
BR (1) BR8305421A (fr)
CA (1) CA1185837A (fr)
CS (1) CS251074B2 (fr)
DD (1) DD208532A5 (fr)
DE (1) DE3367501D1 (fr)
DK (1) DK159480C (fr)
ES (1) ES520128A0 (fr)
GR (1) GR78096B (fr)
HU (1) HU200287B (fr)
IL (1) IL67979A0 (fr)
IN (1) IN156304B (fr)
MX (1) MX156311A (fr)
NZ (1) NZ203392A (fr)
PH (1) PH19096A (fr)
PL (1) PL143926B1 (fr)
PT (1) PT76282A (fr)
RO (1) RO86455B (fr)
WO (1) WO1983002906A1 (fr)
YU (1) YU43155B (fr)
ZA (1) ZA831305B (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0205978A1 (fr) * 1985-05-30 1986-12-30 Pennwalt Corporation Systèmes polymères polyhydroxyliques de délivrance
EP0145846A3 (en) * 1983-12-01 1987-11-19 Pennwalt Corporation Polyhdroxy polymer delivery system
EP0594785A4 (en) * 1991-07-16 1994-07-20 Us Agriculture Methods and compositions of adherent starch granules for encapsulating pest control agents
US6730722B1 (en) 1998-06-19 2004-05-04 Wacker-Chemie Gmbh Cross-linkable polymer powder compositions
WO2010044834A2 (fr) 2008-10-17 2010-04-22 Appleton Papers Inc. Composition de diffusion de parfum contenant des microcapsules d'alcool polyvinylique reticule par des ions de bore ou de persulfate et procede d'utilisation associe

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US5340593A (en) * 1981-10-27 1994-08-23 Union Oil Company Of California Stabilized solid thiocarbonate
US4440746A (en) * 1982-10-28 1984-04-03 Pennwalt Corporation Granular pesticide composition
US4923506A (en) * 1983-12-01 1990-05-08 Pennwalt Corporation Polyhydroxy polymer delivery systems
US4663286A (en) * 1984-02-13 1987-05-05 Damon Biotech, Inc. Encapsulation of materials
US4708861A (en) * 1984-02-15 1987-11-24 The Liposome Company, Inc. Liposome-gel compositions
US5008109A (en) * 1984-05-25 1991-04-16 Vestar, Inc. Vesicle stabilization
US4690825A (en) * 1985-10-04 1987-09-01 Advanced Polymer Systems, Inc. Method for delivering an active ingredient by controlled time release utilizing a novel delivery vehicle which can be prepared by a process utilizing the active ingredient as a porogen
US4755397A (en) * 1986-12-24 1988-07-05 National Starch And Chemical Corporation Starch based particulate encapsulation process
US4812445A (en) * 1987-02-06 1989-03-14 National Starch And Chemical Corporation Starch based encapsulation process
US4853168A (en) * 1987-12-23 1989-08-01 National Starch And Chemical Corporation Process for spinning starch fibers
US5023080A (en) * 1988-06-17 1991-06-11 Basic Bio Systems, Inc. Time release protein
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US5190677A (en) * 1988-10-04 1993-03-02 Union Oil Comany Of California Methods for producing stabilized solid thiocarbonate compositions
US5069831A (en) * 1988-12-22 1991-12-03 The Mead Corporation Method for separation of microcapsules and preparation of printing inks
US5461027A (en) * 1989-01-24 1995-10-24 Griffin Corporation Microencapsulated pendimethalin and method of making and using same
US5160530A (en) * 1989-01-24 1992-11-03 Griffin Corporation Microencapsulated polymorphic agriculturally active material
US5049182A (en) * 1989-02-03 1991-09-17 Ici Americas Inc. Single-package agricultural formulations combining immediate and time-delayed delivery
US4975224A (en) * 1989-03-13 1990-12-04 Pringle Thomas G Process for encapsulation of oily liquid waste materials
GB8918601D0 (en) * 1989-08-15 1989-09-27 British Textile Tech Micro-encapsulation method
US5063164A (en) * 1990-06-29 1991-11-05 Quantum Group, Inc. Biomimetic sensor that simulates human response to airborne toxins
JPH07501082A (ja) * 1992-06-24 1995-02-02 ホット　ペッパー　ワックス　インコーポレーテッド 有機殺虫剤
US5516520A (en) * 1992-07-31 1996-05-14 Industrial Technology Research Institute Controlled-release pesticides and methods for preparation and use thereof
US6090925A (en) 1993-03-09 2000-07-18 Epic Therapeutics, Inc. Macromolecular microparticles and methods of production and use
US5981719A (en) * 1993-03-09 1999-11-09 Epic Therapeutics, Inc. Macromolecular microparticles and methods of production and use
US5750128A (en) * 1994-04-21 1998-05-12 Weed-Master Western Inc. Pesticide composition
US5599767A (en) * 1994-05-27 1997-02-04 Micro Flo Company Salt sensitive binder system
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EP0205978A1 (fr) * 1985-05-30 1986-12-30 Pennwalt Corporation Systèmes polymères polyhydroxyliques de délivrance
EP0594785A4 (en) * 1991-07-16 1994-07-20 Us Agriculture Methods and compositions of adherent starch granules for encapsulating pest control agents
US6730722B1 (en) 1998-06-19 2004-05-04 Wacker-Chemie Gmbh Cross-linkable polymer powder compositions
WO2010044834A2 (fr) 2008-10-17 2010-04-22 Appleton Papers Inc. Composition de diffusion de parfum contenant des microcapsules d'alcool polyvinylique reticule par des ions de bore ou de persulfate et procede d'utilisation associe
EP2364205A4 (fr) * 2008-10-17 2014-09-03 Appvion Inc Composition de diffusion de parfum contenant des microcapsules d'alcool polyvinylique reticule par des ions de bore ou de persulfate et procede d'utilisation associe

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IL67979A0 (en) 1983-06-15
MX156311A (es) 1988-08-09
PH19096A (en) 1986-01-02
DD208532A5 (de) 1984-04-04
KR840003411A (ko) 1984-09-08
DK83583A (da) 1983-08-27
GR78096B (fr) 1984-09-26
ES8403739A1 (es) 1984-04-01
DE3367501D1 (en) 1987-01-02
HU200287B (en) 1990-05-28
DK159480C (da) 1991-03-25
AU1339883A (en) 1983-09-08
WO1983002906A1 (fr) 1983-09-01
DK159480B (da) 1990-10-22
DK83583D0 (da) 1983-02-24
RO86455B (ro) 1985-03-31
PT76282A (en) 1983-03-01
PL143926B1 (en) 1988-03-31
CS124683A2 (en) 1985-06-13
RO86455A (fr) 1985-03-15
BR8305421A (pt) 1983-12-27
CS251074B2 (en) 1987-06-11
EP0088552B1 (fr) 1986-11-12
NZ203392A (en) 1985-08-30
YU41983A (en) 1986-02-28
KR880002503B1 (ko) 1988-11-26
BG43351A3 (en) 1988-05-16
AU564907B2 (en) 1987-08-27
PL240785A1 (en) 1984-03-26
US4439488A (en) 1984-03-27
CA1185837A (fr) 1985-04-23
JPS59500263A (ja) 1984-02-23
ES520128A0 (es) 1984-04-01
YU43155B (en) 1989-04-30
ZA831305B (en) 1985-02-27
IN156304B (fr) 1985-06-15

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